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Preparation method of 5-aryl-1,2,4-triazine-3,6-diformate and application thereof

A technology of diformate and triazine, applied in the field of chemical biology, can solve the problems of low total product yield, low yield and the like

Active Publication Date: 2018-07-17
TIANJIN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] But the productive rate of above-mentioned preparation method is low, and product total yield is lower than 12%, so developing new synthetic method is of great significance in the field of chemical biology

Method used

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  • Preparation method of 5-aryl-1,2,4-triazine-3,6-diformate and application thereof
  • Preparation method of 5-aryl-1,2,4-triazine-3,6-diformate and application thereof
  • Preparation method of 5-aryl-1,2,4-triazine-3,6-diformate and application thereof

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preparation example Construction

[0030] The present invention provides a kind of preparation method of 5-aryl-1,2,4-triazazine-3,6-dicarboxylate, comprising: S-1) ethyl diazo shown in formula (I) Ester and the glycine ester aromatic aldimine shown in formula (II) react under the condition that silver salt catalyst and inorganic base exist, obtain the intermediate shown in formula (III); S-2) described formula (III) ) is mixed with an oxidizing agent for oxidation reaction to obtain 5-aryl-1,2,4-triazazine-3,6-dicarboxylate described in formula (IV);

[0031] N 2 CHCO 2 R 1 Formula (I);

[0032]

[0033] Among them, R 1 with R 2 Each independently is a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C6-C20 aromatic group; preferably a substituted or unsubstituted C1-C8 C10 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C15 aryl; more preferably substituted or unsubstituted C1-C...

Embodiment 1

[0053] Example 1: Methyl 5-phenyl-1,2,4-triazazine-3,6-dicarboxylate

[0054]

[0055] Step 1: Preparation of methyl 5-phenyl-1,2,5,6-tetrahydro-1,2,4-triazazine-3,6-dicarboxylate

[0056] In a dry Schlenk reaction flask (100 mL) was added glycine methyl benzaldimine (0.71 g, 4 mmol), AgOAc (67 mg, 0.4 mmol) and Cs 2 CO 3 (1.30g, 4mmol), 15mL of tetrahydrofuran was added to the system, and stirred at room temperature for 3 minutes; then a tetrahydrofuran solution of methyl diazoacetate (0.36mL, 4mmol) was added to the system, and stirred at 60°C for 24 hours. After the reaction was complete as detected by TLC, the solvent was removed under reduced pressure; then 40 mL of ethyl acetate and 20 mL of water were added to the system for liquid separation, and the aqueous phase was extracted with ethyl acetate (10 mL×3), and the organic phases were combined and washed with water (20 mL). twice, anhydrous MgSO 4 Drying, column chromatography (eluent: petroleum ether / ethyl aceta...

Embodiment 2

[0061] Example 2: Methyl 5-(4-methylphenyl)-1,2,4-triazazine-3,6-dicarboxylate

[0062]

[0063] Step 1: Preparation of methyl 5-(4-methylphenyl)-1,2,5,6-tetrahydro-1,2,4-triazazine-3,6-dicarboxylate

[0064] Add glycine methyl ester-(4-methylbenzaldehyde)imine (0.76g, 4mmol) to a dry Schlenk reaction flask (100mL), Ag 2 O (184mg, 0.8mmol) and K 2 CO 3 (1.10g, 8mmol), add 15mL of acetonitrile to the system, stir at room temperature for 3 minutes; then add a solution of methyl diazoacetate in acetonitrile (0.36mL, 4mmol), and stir at 40°C for 30 hours. After the reaction was complete as detected by TLC, the solvent was removed under reduced pressure; then 40 mL of ethyl acetate and 20 mL of water were added to the system for liquid separation, and the aqueous phase was extracted with ethyl acetate (10 mL×3), and the organic phases were combined and washed with water (20 mL). twice, anhydrous MgSO 4 Drying, column chromatography (eluent: petroleum ether / ethyl acetate = 5 / ...

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Abstract

The invention provides a preparation method of 5-aryl-1,2,4-triazine-3,6-diformate. The method comprises the following steps: S1) allowing diazoacetate of the formula (I) to react with glycine ester aromatic aldimines of the formula (II) in the presence of a silver salt catalyst and an inorganic base, so that an intermediate represented by formula (III) is obtained; S2) mixing the intermediate represented by the formula (III) with an oxidizing agent to carry out oxidation reaction to obtain 5-aryl-1,2,4-triazine-3,6-diformate represented by formula (IV). Compared with the prior art, the methodhas the advantages of less reaction steps and relatively high area selectivity and yield.

Description

technical field [0001] The invention belongs to the technical field of chemical biology, and in particular relates to a preparation method and application of 5-aryl-1,2,4-triazazine-3,6-dicarboxylate. Background technique [0002] 5-aryl-1,2,4-triazazine-3,6-dicarboxylates are an important class of nitrogen-containing heterocycles. As early as 1985, Boger et al. in the United States used ethyl diazoacetate as raw material to obtain 5-aryl-1,2,4-triazazine-3,6-dicarboxylic acid methyl ester with specific structure through five-step reaction, and then It is used for the total synthesis of natural product Streptonigrin (J.Am.Chem.Soc.1985,107,5745-5754)), and the reaction pathway is as follows: [0003] [0004] However, the yield of the above-mentioned preparation method is low, and the total yield of the product is lower than 12%. Therefore, the development of a new synthesis method is of great significance in the field of chemical biology. Contents of the invention ...

Claims

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Application Information

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IPC IPC(8): C07D253/07C07D401/04C07D405/04G01N21/31
CPCC07D253/07C07D401/04C07D405/04G01N21/314G01N2021/3155
Inventor 马军安任楠陈振张发光
Owner TIANJIN UNIV
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